JP2749876B2 - Stable aqueous dispersion of epoxy resin, its production method and its use - Google Patents

Abstract

The invention relates to a stable epoxy resin dispersions and also a process for the preparation thereof and the use thereof, in particular for coatings. The epoxy resin dispersions which are remarkable, in particular, for good storage stability with a low content of organic solvents at the same time and little tendency to skin formation and yield coatings with good surface properties, contain, in addition to water, optionally small quantities of organic solvents and also optionally usual additives, as an essential constituent a condensation product of (a) 50 to 80% by weight of an epoxy compound containing at least two epoxy groups per molecule and having an epoxy equivalent to of 100 to 2,000. (b) 35 to 17% by weight of an aromatic polyol and (c) 15 to 3% by weight of a condensation product of an aliphatic polyol with a molecular weight (Mw) of 200 to 20,000, an epoxy compound containing at least two epoxy groups per molecule and having an epoxy equivalent of 100 to 2,000, and of a mono- and/or polyisocyanate, the equivalent ratio of the OH groups to the epoxy groups being 1:0.85 to 1:3.5, the quantity of mono- and/or polyisocyanate being 0.05 to 5% by weight, referred to the quantity of aliphatic polyol and epoxy compound, and the epoxy equivalent of said condensation product being between 200 and at least 50,000.

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to an aqueous epoxy resin dispersion, a method for producing the same, and uses thereof.

[Problems to be Solved by the Prior Art and the Invention] A synthetic resin is produced by emulsion polymerization, and a stable aqueous dispersion of this resin is produced by adding a solid resin and a suitable dispersant to water with stirring. What is possible is known. However, in the case of a condensate such as an epoxy resin, it must be produced by dispersing a solid resin in water. Such dispersions are generally quite unstable and even settle out in a short time. It also generally exhibits quite poor film forming properties. These disadvantages, namely the low stability of the dispersion and the film-forming properties, are mainly due to the large particle size of the resin.

A method for preparing a coating material based on a polyexide dispersion is disclosed in U.S. Pat.No. 3,772,228, which discloses that a thermosetting one-component coating material comprises a fragile solid polyexide, a fragile solid epoxy curing agent, For example, it is prepared by milling and dispersing a polyanhydride, and optionally an epoxy cure accelerator, in a liquid that is not a solvent for the various components. In this connection, aliphatic hydrocarbons are particularly advantageous. In this way, an epoxy resin dispersion is obtained which is non-aqueous and with the risks associated with using hydrocarbon solvents.

It has an average particle size of less than about 10 μm and a relatively low molecular weight (200 to 4,000, especially 24
Processes for the preparation of organic solvent-free, stable aqueous dispersions of epoxy resins (0 to 1,300) are also known (U.S. Pat. No. 3,879,324). In this case, the epoxy resin is heated to form a melt, mixed with water and a dispersant, and then passed through a colloid-mill. Only epoxy resins of such molecular weight that melt below 100 ° C. of the boiling point of water can be dispersed in this way. This tight limitation has the disadvantage of eliminating many useful epoxy resin systems of high molecular weight. Apart from this, dispersion at the boiling point of water results in still relatively large particles which settle quickly.

The preparation of solid epoxy resins which can be obtained directly in the form of aqueous dispersions has also been disclosed (US Pat.
4,122,067). In this case, a block polymer consisting of ethylene oxide and polypropylene glycol or a weight ratio of polyethylene glycol having a molecular weight of 2,000 to 20,000 and polyglycidyl ether of a polyphenol having a molecular weight of 300 to 2,000 in a molar ratio of 2: 1 to 6: 5. Coalescence has been used as a dispersant. Even with this method, only a dispersion having a particle size of 1 to 3 μm can be obtained.

According to EP 81,163, polyalkylene glycol derivatives are used as nonionic dispersants for stable aqueous dispersions of epoxy resins, with an average particle size of less than 1 μm being possible. However, the coatings obtainable with this dispersion do not yet fully satisfy many properties.

According to European Patent Application Publication No. 51,483,
An epoxy resin dispersion is obtained from a self-emulsifying epoxy resin containing polyoxyalkylene-glycol glycidyl ether and optionally monoepoxide as a reactive thinner. About 3 μm is described as the maximum particle size. Films made from these dispersions and hardeners have relatively soft surfaces because they contain highly inert polyoxyalkylene-glycol-glycidyl ethers and monoepoxides which act as chain stoppers. have.

According to U.S. Pat.No. 4,399,242, an epoxy resin is reacted with diisocyanate at about 120 DEG C. and mixed with water before mixing with an ethylene oxide- and propylene oxide-block polymer diglycidyl ether as emulsifier to be incorporated. Are dispersed. Similarly, the size of the dispersed particles is on the order of 1-3 μm. The film forming properties are also unsatisfactory.

The earlier European Patent Application No. 87.118,640.9 discloses a special self-emulsifying epoxy resin which already has a good storage stability and at the same time has a low organic solvent content and produces a coating with good surface properties. An aqueous dispersion based on is provided. However, under certain conditions, the dispersion has a tendency to form skin.

The invention comprises, in addition to water (B), optionally up to 15% by weight, based on the total dispersion, of an organic solvent (C) and, if appropriate, customary additives (D). In an aqueous dispersion based on a self-emulsifying epoxy resin (A),
A self-emulsifying epoxy resin (A) having an epoxy equivalent of from 250 to 10,000 and a) an epoxy compound containing at least two epoxy groups per molecule and having an epoxy equivalent of from 100 to 2,000
50-80% by weight, especially 55-70% by weight, b) 35-17% by weight of aromatic polyol, especially 35-20% by weight
And c) from aliphatic polyols having an average molecular weight ( _Mw ) of from 200 to 20,000, epoxy compounds containing at least two epoxy groups per molecule and having an epoxy equivalent of from 100 to 2,000 and mono- and / or poly-isocyanates. 15 to 3% by weight, in particular 9 to 4% by weight, of the condensation product
The equivalent ratio of OH-groups to epoxy groups is 1: 0.85 to 1: 3.5, and the amount of mono- and / or poly-isocyanate is 0.05 to 5% by weight based on the total amount of aliphatic polyol and epoxy compound. And wherein the epoxy equivalent of the condensation product is between 200 and at least 50,000.

The invention furthermore relates to the self-emulsifiable epoxy resins A) by first converting the three components A (a), A (b) and A (c) at elevated temperature in the presence of a condensation catalyst and optionally an organic solvent C). , Followed by the addition of, if appropriate, further organic solvents C) and then the addition of water corresponding to the solution thus obtained and, if appropriate, the compounds suitable for D) in the range of 30 to 100. The present invention also relates to a method for producing the above-mentioned epoxy resin dispersion, which is characterized by being added under vigorous stirring at a temperature of ° C.

Finally, the invention also relates to the use of the above-mentioned epoxy resin dispersions in the production of paints, coatings, molding materials and thermosetting materials.

The self-emulsifying epoxy resins corresponding to A) of the dispersions according to the invention preferably have an epoxy equivalent of from 350 to 2,500, in particular from 450 to 1,500. The average particle size of the dispersed resin is generally not larger than 1.0 μm, and 0.3 to 1.0 μm, especially 0.3 to 1.0 μm.
Advantageously, it is 0.8 μm. The proportion of such resins in the overall dispersion is generally about 20 to 70% by weight, in particular 25 to 55% by weight. The term "self-emulsifying" means that no external emulsifier is needed to maintain a stable dispersion of the self-emulsifying resin due to the increased number of molecular chains acting as internal emulsifiers .

The 1,2-epoxy compounds corresponding to A (a) and A (c) are polyepoxides having an average of at least two epoxy groups per molecule. Such epoxy compounds may be saturated or unsaturated, and may be aliphatic-, alicyclic-, aromatic or heterocyclic, which may have a hydroxyl group. They may also contain substituents which do not cause disturbing side reactions under the conditions of the mixing or the reaction, such as alkyl substituents, aryl substituents, ether groups and the like.

These epoxy compounds include polyhydric, especially dihydric alcohols, phenols, hydrogenation products of said phenols and / or monohydric or dihydric phenols in the presence of novolak-acidic catalysts. Preference is given to polyglycidyl ethers based on products of reaction with aldehydes, especially formaldehyde. The epoxy equivalent of the epoxy compound is preferably 160 to 500, particularly preferably 170 to 250. The polyhydric phenols include the following compounds: resorcin, hydroquinone, 2,2-bis- (4-
(Hydroxyphenyl) -propane (bisphenol A), an isomer mixture of dihydroxydiphenylmethane (bisphenol F), tetrabromobisphenol A, 4,4′-dihydroxydiphenylcyclohexane,
4,4'-dihydroxy-3,3'-dimethylphenylpropane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenol, bis- (4-hydroxyphenyl) -1,1-ethane, bis- (4-hydroxyphenyl) -1,1-isobutane, bis- (4-hydroxy-tert-butylphenyl) -2,2-propane, bis- (2-
(Hydroxynaphthyl) -methane, 1,5-dihydroxynaphthalene, tris- (4-hydroxyphenyl) -methane, bis- (4-hydroxyphenyl) -ether, bis- (4-hydroxyphenyl) -sulfone and the above compounds Chlorinated and brominated products. Bisphenol A is particularly advantageous in this connection.

Polyglycyl ethers of polyhydric alcohols are also suitable. Examples of such polyhydric alcohols include the following compounds: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, polyoxypropylene glycol (n = 1 to 1).
0), 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, glycerol and bis- (4-hydroxycyclohexyl) -2,2-propane.

Also, epichlorohydrin or a similar epoxy compound is an aliphatic-, alicyclic- or aromatic polycarboxylic acid,
For example, polyglycidyl of polycarboxylic acid obtained by reacting with oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, 2,6-naphthalenecarboxylic acid and dimeric linolenic acid Esters can also be used. For example, diglycidyl adipate, diglycidyl phthalate and diglycidyl hexahydrophthalate.

A suitable epoxy compound is AMpaquin's "Epoxidverbin"
dungen und Epoxidharze [epoxy compounds and epoxy resins], a handbook, Springer publisher,
Berlin 1958, Chapter IV and Lee and Neville's “Hand
book of Epoxy Resins ", 1967, Chapter 2. Mixtures of several epoxy compounds can also be used.

Examples of the aromatic polyol corresponding to A (b) include A
Compounds containing an OH group and having an aromatic ring, as described in the case of (a) and A (c), for example polyhydric, especially dihydric phenols, chlorinated and bromine thereof Preference products and / or novolaks are preferred. Advantageously, the OH group is directly attached to the aromatic ring. Here too, bisphenol A is particularly advantageous.

The aliphatic polyols of compound A (c) are from 600 to 12,000
Polyether polyols (polyalkylene glycols) having an average molecular weight of 0, especially 2,000 to 8,000 (M _w : measured by gel permission chromatography using polystyrene as a standard) and an OH value of 10 to 200, especially 15 to 16 Is preferred. Advantageously, the polyether-polyols have terminal OH groups at the ends. For example, block copolymers of ethylene oxide and propylene oxide and block copolymers of polyethylene, polypropylene and polybutylene-glycol are mentioned here. Mixtures of the individual polyalkylene glycols can also be used. Advantageously, polyethylene glycol is used.

In the case of the condensation products A (c), c1) the equivalent ratio of OH— groups to epoxy groups is 1: 0.85 to 1: 1.5, in particular 1: 0.95 to 1: 1.20.
With an epoxy equivalent of at least 100,000, especially 100,0
00 to 400,000 or c2) the equivalent ratio is 1: 1.8 to 1:
3.5, especially 1: 2.0-1: 2.6 and epoxy equivalent is 400-1
Preferably it is 0,000.

The condensation products A (c) can be prepared, for example, by subjecting the polyether polyols and polyglycidyl ethers to high temperatures, in particular 50 to 200 ° C., in particular
It can be obtained by condensation at 0-150 ° C .: boron trifluoride and this, for example, with water, phosphoric acid, acetic acid (1: 1 and 1: 2), methanol, diethyl ether, tetrahydrofuran, phenol, tricresylphos. Fart, ethylene glycol monoethyl ether, polyethylene glycol (molecular weight 200), dimethyl sulfoxide, di-
Aqueous or organic solutions of n-butyl ether, di-n-hexyl ether and succinic acid or boron tetrafluoride and complex salts. However, Lewis acids with various bases, such as SnCl
₄ , also suitable. Of these catalysts, BF ₃ - diethyl ether, BF ₃ - it is advantageous to use acetic acid and tetrafluoroboric acid. The amount of catalyst is generally 0,5 based on the reaction mixture.
It is from 1 to 5, especially from 0.15 to 1% by weight. For a good metering, the catalyst is dissolved in a solvent such as diethyl ether, glycol ethers or cyclic ethers, ketones or similar compounds, especially dioxane or methyl isobutyl ketone, from 0.5 to 20% by weight, in particular from 2.5 to 20% by weight. Dilute to a concentration of 12.5% by weight.

In this connection, the two components have an equivalent ratio of OH-groups to epoxy groups of generally from 1: 0.85 to 1: 1.15, especially 1: 0.95.
Use in such an amount that it is ~ 1: 1.20.

Preferred condensation products (dispersants) A (c) are those of the abovementioned epoxy compounds, in particular those of polyglycidyl ethers of bisphenols and aliphatic polyols, the epoxy equivalents of which are determined by the catalyst c1) If used, at least 50,000, in particular at least 100,000, in particular 1
It is between 00,000 and 400,000.

If BF ₃ is used as a more stable complex salt (-→ c2), for example a complex salt with amines, as a special catalyst, both components are preferably OH- to produce the condensation product A (c).
The equivalent ratio of the group to the epoxy group is from 1: 1.8 to 1: 3.5, especially 1: 2.0
Use in such an amount that it is ~ 1: 2.6. Suitable catalysts for this process, pK _b of the reaction was dissolved in a mixture and an amine to form a complex salt in aqueous solution from 15 to 4.5 - the value is from 15 to 4.5 BF ₃ -
It is an amine complex salt. Suitable BF ₃ -amine complexes include, for example, those formed from the following amines (pK _b -values in parentheses) and BF ₃ : n-amylamine (10,63), aniline (4.63), β -Phenylalanine (= 2-amino-
Ethyl-benzene) (9.84), 2-ethylbenzimidazole (6.18), benzylamine (9.33), transbornylamine (10.17), 1-amino-3-methylbutane (10.60), 1,4-diaminobutane (11.15) ), N-butylamine (10.77), tert-butylamine (10.83),
n-butylcyclohexylamine (11.23), cyclohexylamine (10.66), n-decylamine (10.64),
Diethylamine (10.49), diisobutylamine (10.9
1), diisopropylamine (10.96), dimethylamine (10.73), n-dodecanamine (= laurylamine) (1
0.63), 2-aminoethanol (9.50), ethylamine (10.81), hexadecaneamine (10.63), 1-aminoheptene (10.66), 2-aminoheptane (10.88), n
-Hexylamine (10.56), 2,4-dimethylimidazole (8.36), morpholine (8.33), methylamine (10.6
6), n-nonylamine (10.64), octadecaneamine (10.60), octylamine (10.65), 3-aminopentane (10.59), 3-amino-3-methylpentane (11.
01), n-pentadecylamine (10.61), piperazine (9.83), propylamine (10.71), pyrrolidine (11.
27), tetradecaneamine (= myristylamine) (1
0.62), tridecaneamine (10.63), triethylamine (11.01), trimethylamine (9.81).

BF ₃ - benzylamine, BF ₃ - monoethylamine, BF ₃
- it is advantageous to use propylamine and BF _{3-n-butylamine.} However, for example, Anchor Chemi
"Anchor" 1040 (15
16% of the BF ₃ content) or "Anchor" 1171 (11~12% of BF
Also suitable are BF ₃ -amine complex salts which have been liquefied by modification as are commercially available under the name ₃ ).

The reaction between the hydroxyl group and the epoxy group can be carried out at a temperature in the range of 20 to 200 ° C. The reaction temperature is BF ₃ concerned - is dependent on the amine complex. For example BF ₃ - monoethylamine or BF ₃ - reaction temperature when using benzylamine is 130 to 140 ° C., in the case of using a liquefied amine complex salts is about 170 ° C.. Therefore, the mixture to be reacted, consisting of compounds containing hydroxyl and epoxy groups, is advantageously heated to a temperature at which the reaction proceeds at a suitable rate (i.e. 30 minutes to 15 hours). The reaction advantageously follows an increase in epoxy equivalent indicating a decrease in epoxy groups. The reaction can be stopped by cooling below the reaction temperature. Part of the BF ₃ -amine complex is consumed during the reaction until fluoride ions are introduced into the reaction product. Some excess BF ₃ -amine complex is a substance with basic activity,
Detoxification can be achieved after the reaction is completed, for example, by adding excess soil, calcium oxide, calcium hydroxide, barium oxide and barium hydroxide to the complex salt. Substance having basic activity this compound and BF ₃ by filtration - except with product resulting from the amine complex salt.

The amount of these catalysts c2) is generally likewise from 0.1 to 5, in particular from 0.15 to 1 part by weight, based on the reaction mixture. To further improve the metering, the catalyst is added in a suitable solvent for 0.5
It may be diluted to -10% by weight, especially 2.5-12.5% by weight.

Advantageous condensation products (dispersants) A (c) produced using the above-mentioned catalysts c2) are the condensation products of aliphatic polyols with the above-mentioned epoxy compounds, in particular the polyglycidyl ethers of bisphenols, The epoxy equivalent of the condensation product is from 200 to 120,000, in particular from 400 to 10,000.

Suitable monoisocyanates for preparing component Ac) are, for example, those which contain substantially only one isocyanate group, for example methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, n-dodecyl isocyanate , Phenyl isocyanate, α-naphthyl isocyanate and the like. In addition, mention may also be made of partially blocked polyisocyanates which still have free NCO-groups. The compounds mentioned below may be suitable as polyisocyanates. Blocking agents are monohydric alcohols of aliphatic, cycloaliphatic or alkylaromatics, such as lower aliphatic alcohols such as methyl- and ethyl alcohol, various propyl-, butyl- and hexyl alcohols,
Heptyl-, octyl-nonyl-, decyl- and dodecyl-alcohols and analogs thereof; methoxy-
(1- or 2-) propanol; further unsaturated alcohols such as allyl alcohol and propargyl
alicyclic alcohols such as cyclopentanol, cyclohexanol; alkyl aromatic alcohols such as benzyl alcohol, methyl and also p-methoxy and p-nitrobenzyl alcohol; and monoethers of glycols And the corresponding monoethers of, for example, ethylene glycol-monomethyl ether, ethylene glycol-monoethyl ether, ethylene glycol-monobutyl ether or propylene glycol. In this case, ethylene glycol,
Preference is given to 2-ethylhexanol, butyldiglycol, butylglycol and benzyl alcohol, especially alcohols which form liquid semi-urethanes.

As polyisocyanates, in particular diisocyanates, there are the customary polyisocyanates known in the polyurethane or coatings art, for example aliphatic, cycloaliphatic or aromatic polyisocyanates. Representative examples of such polyisocyanates include: tolylene-2,4-diisocyanate and technical mixtures thereof with toluylene-2,6-diisocyanate;
Toluylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene-1,6-
Diisocyanate, naphthalene-1,5-diisocyanate, m-xylene diisocyanate, 1-methyl-2,4
-Diisocyanate cyclohexane, isophorone diisocyanate, 2,4,4-trimethyl-1,6-diisocyanatehexane, dimeric toluylene-2,4-diisocyanate, N, N'-di- (4-methyl-3-isocyanatephenyl ) Urea, N, N ', N "-tri- (6-isocyanatohexyl) -buret, triphenylmethane-4,
4 ', 4 "-triisocyanate, 3 moles of toluylene-
Reaction product of 2,4-diisocyanate with 1 mole of 1,1,1-trimethylolpropane, trimer or polymer product of toluylene-2,4-diisocyanate, toluylene-
A mixed trimer or copolymer product of 2,4-diisocyanate and hexamethylene-1,6-diisocyanate, an isomer mixture of diphenylmethane isocyanates, containing two or more benzene nuclei linked via a methane group And a diisocyanate having a diphenylmethane structure in which a part of the isocyanate group is converted to a carbodiimide group.

It is particularly advantageous to use isomers of phenyl isocyanate, toluylene diisocyanate or mixtures thereof, isomers of isophorone diisocyanate and trimethylhexamethylene diisocyanate or mixtures thereof.

The reaction with the above isocyanates is carried out at 50-140 ° C., especially at 110 ° C.
It can be carried out in a temperature range of 135135 ° C. for a period of from 15 to 400 minutes, in particular from 30 to 60 minutes, optionally in the presence of solvents and catalysts which are inert towards isocyanates. Again, in the case of poly (di) isocyanates, care must be taken to avoid gelling by selecting appropriate reaction conditions, especially the quantitative ratio.

Solvents which are inert towards isocyanates and which are optionally removed by distillation after the end of the reaction include:
For example, esters, such as ethyl acetate, butyl acetate, methyl glycol acetate and ethyl glycol acetate; ketones, such as methyl ethyl ketone, methyl isobutyl ketone; aromatic compounds, such as mixtures of toluene, xylene and higher aromatic compounds; There is a mixture of Toluene and xylene are particularly preferred.

The above-mentioned catalysts are common catalysts in isocyanate chemistry, for example tertiary amines and / or compounds of divalent and tetravalent tin, such as diazobiscyclooctane (DABCO), tin (II) octoate, dibutyl There are tin oxide, dibutyltin dioctoate, dibutyltin dilaurate and the like. In this connection, dibutyltin dilaurate is particularly advantageous.

The amount of isocyanate is generally from 0.05 to 5% by weight, in particular from 0.1 to 2.5% by weight, in particular from 0.1 to 1.0% by weight, based on the aliphatic polyol and the epoxy compound in Ac).
If a poly (di) isocyanate is used in the presence of a catalyst, a smaller amount can be used in this context than without a catalyst or with a monoisocyanate. In this case, the isocyanate is reacted with the OH groups of the reaction product of the aliphatic polyol with the epoxy compound (possibly already containing OH groups) and is also present in the reaction product. It can also react with the epoxy group. In this case, after reaction with the isocyanate in Ac), an appropriate number of reactive groups (OH
And / or epoxy groups) are still present, Aa) and
Care should be taken to be able to react with Ab).

The amount of the condensation product A (c) in the self-emulsifying epoxy resin is generally about 3 to 3 based on the self-emulsifying epoxy resin.
15% by weight, in particular 4 to 9% by weight.

Advantageously, the amount of water in the dispersion according to the invention is about 30 to 55% by weight, in particular about 35 to 50% by weight, based on the total dispersion.

Suitable organic solvents corresponding to component C) of the dispersions according to the invention are, in particular, ethylene glycol mono- or -diethers of monoalcohols, optionally with branched alkyl radicals having 1 to 6 carbon atoms, propylene glycol mono- Or -diethers, butylene glycol mono- or -diethers; aliphatic alcohols having optionally branched alkyl groups of 1 to 12 carbon atoms; aromatic aliphatic or alicyclic alcohols, such as benzyl alcohol Or cyclohexanol; an aromatic compound,
For example, xylene; or ketones such as methyl isobutyl ketone, and these solvents can be used alone or in a mixed state. The boiling point of the above solvent is 21
Advantageously it is not above 0 ° C. In this connection, particular preference is given to ethyl glycol, methyl glycol, methoxypropanol, ethoxypropanol and / or benzyl alcohol. The epoxy resin dispersion according to the invention contains from about 2 to 15% by weight, in particular from about 4 to 10% by weight, of the abovementioned organic solvents.

Typical additives in the meaning of D), which may optionally be present in the compositions according to the invention, include, for example, the following: common coating additives, for example pigments, pigments Pastes, antioxidants, leveling or thickening agents, defoamers and / or wetting agents, reactive diluents, fillers, catalysts and the like. These additives, including the curing agent and another thermosetting resin, may optionally be added only immediately before processing.

As a curing agent for the self-emulsifying epoxy resin of the present invention, a curing agent or a curable compound (epoxy curing agent) known for this purpose can be used. For example, a basic curing agent (amine-based curing agent) such as polyamine,
There are Mannich bases, addition products of amines added to polymers such as polyepoxides and polyamidoamines. Further, an acidic curing agent (acid curing agent), for example, polycarboxylic acid and its acid anhydride, and polyhydric phenols may be used. Synthetic resins containing hydroxyl and / or amino groups, such as amine or phenolic resins, are also suitable for this purpose.

Basic curing agents (amine-based low-temperature curing agents) suitable for curing at room temperature or at low temperatures are commonly used in an epoxy equivalent: amine hydrogen equivalent-ratio: 1: (0.75 to 1.5), and polyalkyleneamines such as diethylenetriamine, triethylene Ethylenetetramine, tetra-ethylenepentamine and the like and also 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, bis- (3-aminopropyl) methylamine, 1,4-bis- (3- Aminopropyl) -piperazine, N, N-bis (3-aminopropyl) ethylenediamine and also cycloaliphatic amines, for example 1,2- or 1,3-
Diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1,2-diamino-4-ethylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1-cyclohexyl-3,4-diamino- Cyclohexane, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, 2,2-bis (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino- There are dicyclohexylmethane, 3-amino-1-cyclohexaneaminopropane, 1,3- and 1,4-bis (aminomethyl) -cyclohexane.

As araliphatic amines, use is made in particular of those amines in which the amino group is present at the aliphatic residue. For example, m
-And p-xylylenediamine or hydrogenated products thereof. These amines can be used alone or in a mixed state.

Suitable Mannich bases are polyamines, especially diethylenetriamine, triethylenetetramine, isophoronediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis (aminomethyl)-
Cyclohexane, especially m- and p-xylylenediamine and aldehydes, especially formaldehyde, and mono- or polyhydric phenols having at least one aldehyde-reactive site in the nucleus, such as various cresols and xylenols, p -Tert-butylphenol, resorcinol, 4,4'-dihydroxydiphenylmethane, 4,4 '
Prepared by condensation with dihydroxydiphenyl-2,2-propane, especially phenol.

Suitable amine-epoxy addition products are, for example, ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4-, 2,4,4-trimethylhexamethylenediamine, m-xylylenediamine and / or bis-
Diamines such as (aminomethyl) cyclohexane and terminal epoxides such as propylene oxide, hexene oxide or glycidyl ethers such as phenyl glycidyl ether, ethylhexyl glycidyl ether, butyl glycidyl ether or glycidyl esters such as "Cardura E Or reaction products with polyglycidyl ethers or esters as described under A (a) or A (c).

Polyamidoamines which can be used for the purposes of the present invention are obtained, for example, by reacting polyamines with polycarboxylic acids, for example dimerized fatty acids.

In addition to the above-mentioned polyamines, water-soluble polyoxypropylenediamines having a molecular weight of 190 to 2,000 and also hardeners which are easily dispersible in water, such as DE 2,332,177 and EP 605.
Those described in the specification, ie modified amine addition products, are advantageously used as amine-based hardeners. Coatings obtainable from these dispersions may also be heated to 50-120 ° C for 30-120 minutes to achieve sufficient cure.

Suitable oxidative curing agents generally used in an epoxy / carboxyl equivalent ratio of 1: (0.75 to 1.5) are water-soluble polycarboxylic acids, such as cyclopentanetetracarboxylic acid, especially butanetetracarboxylic acid, such as cyclobutanetetracarboxylic acid, In particular, 1,2,3,4-butanetetracarboxylic acid, and also aconitic acid, citric acid or, if appropriate, the acid anhydride or acid of the above acid and the acid with 2 to 12 carbon atoms, especially 2 to 6 carbon atoms. With polyhydric alcohols such as neopentyl glycol, glycerol, trimethylolethane or -propane, alkane-diols and, optionally, their oligomers having one or more ether bridges, such as ethylene glycol, propane- and butanediols Acid esters, and these esters must have at least three free COOH groups have. Also, pyromellitic acid, trimellitic acid, phthalic acid, endomethylenetetra- or -hexahydrophthalic acid, maleic acid, fumaric acid or -as long as they are present-anhydrides thereof and polyhydric alcohols, such as those mentioned above. 3 or more COOH
Group-containing acid esters can also be used as polycarboxylic acid curing agents as long as they have appropriate water solubility or water dilutability. In this connection, note that dibasic carboxylic acids are reacted with at least trihydric alcohols or dihydric alcohols with at least trihydric carboxylic acid in order to obtain an appropriate number of COOH groups in the acidic ester. Should.

Instead of or in addition to the above-mentioned curing agents, amine and / or phenolic resins may be present in the curing reaction in an amount of from 5 to 50% by weight, in particular from 10 to 35% by weight, based on the total solids content. It may be used for the purpose. Optionally, in this case, further water is added to the dispersion so that the total solids content is adjusted to 10-80% by weight. Examples of the amine resin include amine aldehyde resins, that is, condensation products of aldehydes and melamine (melamine resins), condensation products of aldehydes and urea (urea resins), condensation products of aldehydes and acetoguanamine ( There is a condensation product of an acetoguanamine resin) or an aldehyde with an analogous compound of the partner component or a corresponding precursor condensation product. Preferred aldehyde condensation products of melamine include in particular melamine-methylol-alkyl ethers, where the alkyl group is a methyl-, n- or i-butyl group, especially a methyl group, such as hexamethoxymethylmelamine, Ethoxymethoxymethylmelamine, monomethylolpentamethoxymethylenemelamine, dimethyloltetramethoxymethylenemelamine, trimethyloltrimethoxymethylenemelamine and their analogs or corresponding oligomers or polymer products having a substantially monomeric structure It is.

Examples of the phenol resin curing agent include resols, formaldehyde-phenol carboxylic acid resin, and phenol resin intermediate products. In this case, commercially available etherified phenolic resin resols which can be diluted with water are particularly advantageous. In some cases, acidic catalysts such as p-toluenesulfonic acid, cyclohexanesfamic acid, acidic butyl phosphate and phosphoric acid-optionally (amine) salts and-may be added to the phenolic and / or amine resins to effect cure rates. To produce a film or coating that cures at a much lower temperature or for a much shorter time. The amount of acidic catalyst is, for example, up to 2% by weight, based on the total solids content.

Additional curable resins in the sense of component D) are resins which can be dispersed in aqueous media, for example based on hydroxyalkyl-acrylates, hydroxyalkyds, polyesters, epoxy-based resins and the like. It is. The proportion of the additional resin can be determined, for example, such that the solids content of the mixture is about 10 to 80% by weight, in particular 20 to 40% by weight. The properties of the product made from the dispersion can be affected as desired by the addition of such resins. Thus, for example, the presence of an acrylate resin can improve the yellowing resistance of coatings made from the dispersion, and the addition of alkyd resins can improve elasticity.

The total solid content of the epoxy resin dispersion of the present invention is about 10 to
It can be 80% by weight, in particular 35-70% by weight, especially 45-60% by weight. Its viscosity is generally 300-30,000 mPa.s, especially 1,000
77,000 mPa.s (20 ° C.). The epoxy resin dispersion of the present invention is particularly characterized by its good storage stability. This is mainly due to the small content of the organic solvent in the self-emulsifying epoxy resin and the small average particle size. The coating obtained with this dispersion furthermore has a low water sensitivity with improved hardness.

In the process according to the invention for preparing epoxy resin dispersions, the self-emulsifying epoxy resin A) is first prepared by subjecting the three components A (a), A (b) and A (c) to high temperature, generally
It is prepared by condensation at 120 to 220 ° C., especially 150 to 180 ° C. in the presence of a condensation catalyst. Suitable as condensation catalysts are, for example, phosphinic acids, such as triphenylphosphinic acid; phosphonium salts, such as benzyltrimethylphosphonium chloride; tertiary amines, such as benzyldimethylamine; quaternary ammonium salts, such as tetramethylammonium chloride; Metal hydroxides such as NaOH, LiOH; alkali metal carbonates such as sodium carbonate, lithium carbonate; alkali metal salts of organic acids such as sodium formate and lithium benzoate. The organic solvent C) may already be present in whole or in part during the condensation.

The resin is then added to the resin at a temperature of from 120 DEG to 220 DEG C., in particular from 100 DEG to 160 DEG C., to give a solution, if the condensation is not carried out in the presence of all organic solvents. An appropriate amount of water is then added under vigorous stirring at a temperature of 30 to 100 ° C., in particular 55 to 85 ° C., resulting in an aqueous dispersion. The dispersion is carried out using a high-speed impeller, colloid-mill, homogenizer or other high-speed stirrer with high shearing forces, such as a dissolver.

The compound (additive, curing agent, other curable resin) corresponding to D) is preferably added only immediately before use of the dispersion.

The dispersions according to the invention are suitable for the production of coatings and / or intermediate coatings for a very wide variety of fields of application in combination with suitable hardeners, in particular as protective coatings on rough and porous substrates. Are suitable. In addition, it is suitable for chemical and weather resistant coatings and linings of articles.

Due to their advantageous properties, the dispersions according to the invention are clearly suitable for single-layer coatings. This adhesive coating may be as it is, but may also serve as a two-layer primer, in other words, as a subbing for another coating, which may consist of itself or other customary coating materials.

The dispersions according to the invention are also suitable for additional use in electrodeposition coatings because of their good dilutability and their other advantageous properties.

Another possibility is the use of adhesives that can be diluted with water.
It can also be used as a binder for fibers, organic and / or inorganic materials. They are also suitable for curable molding materials. In addition, it is also suitable as an additive for synthetic resin cement.

When used as a coating (or mainly as a water-based paint), substrates, such as metals, wood, glass, concrete, synthetic resins, ceramics, etc., can be applied by customary methods, such as brushing, spraying, dipping or roll coating. Can be painted. When a curing agent is not used for cold curing, the coating is cured for a sufficient time,
It is generally cured by heating to 100-250 ° C for about 5 minutes to about 1 hour.

In the following experiments and examples,% is% by weight. Viscosity was always measured at room temperature with a Brookfield viscometer.

EXAMPLES I. Preparation of Condensation Products (Dispersions) A (c) Using Catalyst c1) In all of Examples I.1 to 11, the reaction mixture is heated to 130 ° C. after addition of the BF ₃ compound. This temperature was maintained until the reaction was completed. The end of the reaction is indicated by an increase in the epoxy equivalent to the respective stated value.

Example I.1 309 g of technical polyethylene glycol with an average molecular weight of 4,000 and 32.5 g of a polyglycidyl ether based on bisphenol A with an epoxy equivalent of 185 are
Heat together to 100 ° C and 50% strength dissolved in H ₂ O
The HBF ₄ 0.5 ml was added under stirring and diluted with methyl isobutyl ketone 10 ml. The OH / epoxy equivalent ratio was 1: 1.15. The condensation product had an epoxy equivalent of about 350,000.
Methyl isobutyl ketone was removed under reduced pressure.

Example I.2 Toluylene-diisocyanate (TDI 80-80% 2.4
2.85 g of isomer, 20% 2,6-isomer) in distilled xylene 10
The solution, dissolved in 3 ml, was added to about 285 g of the condensate according to Example I.1.
Added at 130 ° C. for 0 minutes. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. This condensate is 12,170 in a 50% by weight solution in benzyl alcohol.
It had a viscosity of mPa.s (25 ° C).

Example I.3 A solution of 1.42 g of TDI-80 in 10 ml of distilled xylene was added to 284 g of the condensate according to Example I.1 at 130 ° C. for about 30 minutes. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. This condensate had a viscosity of 8,120 mPa.s (25 ° C.) in a 50% by weight solution in benzyl alcohol.

Example I.4 A solution prepared by dissolving 0.7 g of TDI-80 in 10 ml of distilled xylene was added to a solution of benzyl alcohol at a concentration of 50% by weight.
280 g of the condensate according to Example I.1 having a viscosity of 530 mPa.s (25 ° C.) were added at 130 ° C. in about 30 minutes. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. This condensate in a 50% by weight solution in benzyl alcohol
It had a viscosity of 000 mPa.s (25 ° C.).

Example I.5 A solution prepared by dissolving 2.81 g of phenyl isocyanate in 10 ml of distilled xylene in the form of a 50% strength by weight benzyl alcohol solution according to Example I.1 having a viscosity of 5,530 mPa.s (25 ° C.) To 2.81 g of the condensate was added at 130 ° C. in about 30 minutes. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. This condensate had a viscosity of 5,500 mPa.s (25 ° C.) in a 50% by weight solution in benzyl alcohol.

Example I.6 0.5 ml of a 1% strength solution of dibutyltin dilaurate in xylene and then 1.23 g of solution in 15 ml of distilled xylene
The solution in which TDI-80 was dissolved was added in 30 minutes to 247 g of a condensate according to Example I.1 having a viscosity of 5,530 mPa.s (25 ° C.) in the form of a 50% strength by weight benzyl alcohol solution at 130 ° C. Was added. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. The condensate had a viscosity of 7,680 mPa.s (25 ° C.) in a 50% by weight solution in benzyl alcohol.

Example I.7 0.5 ml of a 1% strength solution of dibutyltin dilaurate in xylene and then a solution of 1.15 g of isophorone diisocyanate in 15 ml of distilled xylene were added in 30 minutes to 50% strength by weight benzyl alcohol. 4,75 in solution
Condensate 2 according to Example I.1 having a viscosity of 0 mPa.s (25 ° C.)
Added to 31 g at 130 ° C. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. In the state of a 50% by weight solution in benzyl alcohol, this condensate was 5,730 mPa.s (25
C).

Example I.8 0.5 ml of a 1% strength solution of dibutyltin dilaurate in xylene and then 1.30 g of trimethylhexamethylene diisocyanate (2,2,4
-And a mixture of 2,4,4-isomers) in a 50% strength by weight benzyl alcohol solution for 30 minutes.
At 130 ° C., 259 g of the condensate according to Example I.1 having a viscosity of 5,530 mPa.s (25 ° C.) were added. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. In the state of a 50% by weight solution dissolved in benzyl alcohol, this condensate was 7,160 mPa.s
(25 ° C.).

Example I.9 1.0 ml of a 1% strength solution of dibutyltin dilaurate in xylene and then 2.6 g of phenylisocyanate in 20 ml of distilled xylene were added in 30 minutes.
4,750 mP in 50% by weight benzyl alcohol solution
259 g of condensate according to Example I.1 having a viscosity of as (25 ° C.)
At 130 ° C. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. 50 dissolved in benzyl alcohol
4,850 mPa.s (25 ° C)
It had a viscosity of

Example I.10 105 ml of a 1% strength solution of dibutyltin dilaurate in xylene and then 3.78 g of phenylisocyanate in 15 ml of distilled xylene were added in 30 minutes.
5,530 mP in 50% by weight benzyl alcohol solution
185 g of condensate according to Example I.1 having a viscosity of as (25 ° C.)
At 130 ° C. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. 50 dissolved in benzyl alcohol
4,240 mPa.s (25 ° C)
It had a viscosity of

Example I.11 250 g of TDI-80 was heated to 60 ° C. under a dry nitrogen atmosphere with stirring. 3 ml of a 1% strength solution of dibutyltin dilaurate in xylene was added. 129.5 g of dry ethyl glycidyl ether are added during 120 minutes. The solution is then kept at 60 ° C. for a further 120 minutes until the NCO-group content of the half-urethane is 15-16% by weight.

Example I.12 0.5 ml of a 1% strength solution of dibutyltin dilaurate in xylene and 4.42 g of the above semi-urethane in 20 ml of distilled xylene were added in a proportion of 50% by weight in 30 minutes.
4,490 mPa.s (25
130 ° C. to 220 g of the condensate according to Example I.1 having a viscosity of
Was added. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. 50% by weight dissolved in benzyl alcohol
This condensate had a viscosity of 5,130 mPa.s (25 ° C.) in a concentrated solution state.

Preparation of condensation products (dispersants) A (c) using the catalysts described under II.c2) Example II.1 Polyethylene glycol 500 with an average molecular weight of 4,000
g and 115.5 g of a polyglycidyl ether based on bisphenol A having an epoxy equivalent of 185
Heated to ° C. Add 2 g of BF ₃ -amine complex “Anchor” 1040 and heat to 170 ° C. The epoxy equivalent was checked. An additional 0.85 g of the amine complex "Ancor" 1040 was added to the three batches. Means 20% higher condensation of the reactants than is equivalent to the hydroxyl group reaction of polyethylene glycol
The reaction is terminated after an epoxy equivalent of 1,940 has been achieved. The OH / epoxy equivalent ratio was 1: 2.5.

Example II.2 Polyethylene glycol 500 with an average molecular weight of 4,000
g and 92.5 g of a polyglycidyl ether based on bisphenol A having an epoxy equivalent of 185 at 120 ° C.
Heat to 2g of BF ₃ - was added monoethylamine, 150
Heat to ° C. Check epoxy equivalent. The reaction was terminated after an epoxy equivalent of 3,140 was reached, meaning condensation of the reactants as high as 25% higher than the equivalent of the hydroxyl groups of the polyethylene glycol. The OH / epoxy equivalent ratio was 1: 2.0.

Example II.3 1.0 ml of a 1% strength solution of dibutyltin dilaurate in xylene and then 6.25 g of 40 ml of distilled xylene
During 30 minutes of the solution in which TDI-80 was dissolved, the condensate corresponding to Example 1 above was added at 130 ° C. After maintaining at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. In the state of a 50% by weight solution dissolved in benzyl alcohol, this condensate is
It has a viscosity of 3,750 mPa.s (25 ° C.) and an epoxy equivalent of 3,750.

Example II.4 A solution of 250 g of isophorone diisocyanate in 20 ml of distilled xylene was added in 30 minutes to 250 g of a condensate having an epoxy equivalent of 2,400 and corresponding to the above example 2 at 130 ° C.
Was added. After holding at 130 ° C. for 60 minutes, xylene was removed under reduced pressure. 50% by weight dissolved in benzyl alcohol
This condensate had a viscosity of 880 mPa.s (25 ° C.) in a concentrated solution state.

III. Examples of Preparation of Dispersions of the Invention Using the Condensation Products as in Examples I.2 to 11. EXAMPLE III.1-3 with a Thermometer, Bladed Stirrer, Reflux Cooler and Dropping Funnel In a single-necked flask, an epoxy resin based on bisphenol A having an epoxy equivalent of 183
5 g were reacted with 98 g of bisphenol A and 27 g of dispersant dissolved in 27 g of benzyl alcohol in the presence of 750 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. Dilution was performed with cooling with 60 g of methoxypropanol. 85 g of deionized water is added uniformly over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / min and a temperature drop to 70 to 60 ° C., further diluted with 163 g of deionized water Was manufactured. This dispersion
Solids content of 53.7% by weight, viscosity of 4,000 mPa.s (Brookfield, spindle 2, 6 rpm) and 0.50
It had a particle size of μm.

Example III.2 Bisphenol A-based epoxy resin with an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, impeller stirrer, reflux condenser and dropping funnel
5 g was reacted with 98 g of bisphenol A and 98 g of dispersant 1.2) dissolved in 27 g of benzyl alcohol in the presence of 750 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 520-530 was achieved. Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with 170 g of deionized water Was manufactured. This dispersion had a solids content of 54.2% by weight, a viscosity of 5,200 mPa.s (Brookfield viscosity, spindle 3, 6 revolutions / min) and a particle size of 0.45 μm.

Example III.3 Bisphenol A-based epoxy resin with an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, a vane stirrer, a reflux condenser and a dropping funnel.
5 g were reacted in the presence of 700 mg of triphenylphosphine with 120 g of bisphenol A and 27 g of dispersant I.4) dissolved in 27 g of benzyl alcohol at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. This dispersion had a solids content of 53.2% by weight, a viscosity of 4,900 mPa.s (Brookfield viscosity, spindle 3, 6 rpm) and a particle size of 0.46 μm.

Example III.4 Bisphenol A-based epoxy resin having an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, impeller stirrer, reflux condenser and dropping funnel
5 g were reacted with 120 g of bisphenol A in the presence of 700 mg of triphenylphosphine and 1.5 g of a dispersant 1.5.27) dissolved in 27 g of benzyl alcohol at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. The dispersion had a solids content of 54.2% by weight, a viscosity of 4,950 mPa.s (Brookfield viscosity, spindle 3, 6 rpm) and a particle size of 0.50 μm.

Example III.5 Bisphenol A-based epoxy resin having an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, a vane stirrer, a reflux condenser and a dropping funnel.
5 g were reacted with 120 g of bisphenol A and 27 g of dispersant I.6) dissolved in 27 g of benzyl alcohol in the presence of 700 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. . Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. This dispersion has a solids content of 53.3% by weight and a viscosity of 4,250 mPa.s (Brookfield viscosity, spindle 3, 6 revolutions /
Min) and a particle size of 0.45 μm.

Example III.6 Bisphenol A based epoxy resin having an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, a vane-type stirrer, a reflux condenser and a dropping funnel.
5 g were reacted with 120 g of bisphenol A and 27 g of dispersant 1.7.7) dissolved in 27 g of benzyl alcohol in the presence of 700 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. . Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. This dispersion has a solids content of 52.9% by weight and a viscosity of 4,500 mPa.s (Brookfield viscosity, spindle 3, 6 revolutions /
Min) and a particle size of 0.39 μm.

Example III.7 Bisphenol A-based epoxy resin with an epoxy equivalent of 183 in a two three-necked flask equipped with a thermometer, impeller stirrer, reflux condenser and dropping funnel
5 g was reacted with 120 g of bisphenol A and 27 g of dispersant I.8) dissolved in 27 g of benzyl alcohol in the presence of 700 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 520-540 was achieved. . Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. This dispersion has a solids content of 54.0% by weight and a viscosity of 4,700 mPa.s (Brookfield viscosity, spindle 3, 6 revolutions /
Min) and a particle size of 0.42 μm.

Example III.8 Bisphenol A-based epoxy resin with an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, impeller stirrer, reflux condenser and dropping funnel
5 g were reacted with 120 g of bisphenol A and 27 g of dispersant I.9) dissolved in 27 g of benzyl alcohol in the presence of 700 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. . Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. This dispersion has a solids content of 53.2% by weight and a viscosity of 4,950 mPa.s (Brookfield viscosity, spindle 3, 12 rpm /
Min) and a particle size of 0.50 μm.

Example III.9 Bisphenol A-based epoxy resin having an epoxy equivalent of 183 in a two three-necked flask equipped with a thermometer, impeller stirrer, reflux condenser and dropping funnel
5 g were reacted with 120 g of bisphenol A and 27 g of dispersant I.10) dissolved in 27 g of benzyl alcohol in the presence of 700 mg of triphenylphosphine at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. . Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. This dispersion has a solids content of 53.2% by weight and a viscosity of 5,000 mPa.s (Brookfield viscosity, spindle 3, 12 revolutions /
Min) and a particle size of 0.44 μm.

Example III.11 Bisphenol A-based epoxy resin with an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, a vane stirrer, a reflux condenser and a dropping funnel.
5 g were reacted with 120 g of bisphenol A in the presence of 700 mg of triphenylphosphine and dispersant I.4) 27 g in 27 g of benzyl alcohol at 150-170 ° C. until an epoxy equivalent of 510-530 was achieved. . Dilution was performed with cooling with 60 g of methoxypropanol. An aqueous dispersion in which 85 g of deionized water is uniformly added over a period of 5 to 30 minutes at a stirring speed of about 800 revolutions / minute and a temperature drop to 70 to 60 ° C., and further diluted with about 215 g of deionized water Was manufactured. The dispersion had a solids content of 53.1% by weight and a viscosity of 2,575 mPa.s (Brookfield viscosity, spindle 2, 12 revolutions /
Min) and a particle size of 0.53 μm.

IV. Example II. Preparation of the Dispersions of the Invention Using the Condensation Products of 3-4 Example IV.1 Two Three Ports Equipped with Thermometer, Bladed Stirrer, Reflux Cooler and Dropping Funnel In a flask, an epoxy resin 32 based on bisphenol A with an epoxy equivalent of 183
5 g were reacted with 98 g of bisphenol A and 27 g of dispersant II.3) dissolved in 27 g of benzyl alcohol in the presence of 600 mg of triphenylphosphine at 150-160 ° C. until an epoxy equivalent of about 530 was achieved. Dilution was performed with cooling with 60 g of methoxypropanol. 85 g of deionized water was added and stirred for 5 minutes at a stirring speed of about 800 rev / min at a temperature below 70 ° C. to produce an aqueous dispersion further diluted with about 235 g of deionized water. The dispersion has a solids content of 53.0% by weight, a viscosity of 650 mPa.s (Brookfield viscosity, spindle 2, 30 rpm) and 0.65 μm
Particle size.

Example IV.2 Bisphenol A-based epoxy resin having an epoxy equivalent of 183 in a two-necked three-necked flask equipped with a thermometer, a vane-type stirrer, a reflux condenser and a dropping funnel.
5 g were reacted with 98 g of bisphenol A and 54 g of dispersant II.4) dissolved in 54 g of benzyl alcohol in the presence of 600 mg of triphenylphosphine at 150-160 ° C. until an epoxy equivalent of about 550 was achieved. Dilution was carried out with cooling with 33 g of methoxypropanol. Add 85 g of deionized water and stir at about 800 rpm for 5 minutes.
Stir below the temperature of 0 ° C. and produce an aqueous dispersion further diluted with about 230 g of deionized water. 52.9% by weight of this dispersion
, A viscosity of 2,900 mPa.s (Brookfield viscosity, spindle 2, 12 rpm) and a particle size of 0.62 μm.

A sample of this dispersion does not form a solid skin when left open for several hours. The viscosity increase resulting from evaporation at the surface can be uniformly stirred.

V. Use test A series of the dispersion according to the invention (Example II.2) and the dispersion according to the prior art (European Patent No. 81,163) is subjected to a use test. The results are shown in Tables 1 and 2 below.

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Claims (21)

(57) [Claims] 1. Self-emulsifying epoxies which, in addition to water (B), optionally contain up to 15% by weight, based on the total dispersion, of an organic solvent (C) and, if appropriate, customary additives (D). In the aqueous dispersion based on the resin (A),
A self-emulsifying epoxy resin (A) having an epoxy equivalent of from 250 to 10,000 and a) an epoxy compound containing at least two epoxy groups per molecule and having an epoxy equivalent of from 100 to 2,000
50-80% by weight, b) an aromatic polyol 35-17% by weight and c) an average molecular weight of 200 to 20,000 (aliphatic polyol having M _W), contains at least two epoxy groups per molecule and 100 to 2,000 of 15 to 3% by weight of a condensation product comprising an epoxy compound having an epoxy equivalent and a mono- and / or poly-isocyanate, provided that the equivalent ratio of the OH group to the epoxy group is 1: 0.85 to 1: 3.5, -And / or
Or, the amount of the poly-isocyanate is 0.05 to 5% by weight based on the total amount of the aliphatic polyol and the epoxy compound.
And wherein the epoxy equivalent of the condensation product is between 200 and at least 50,000. 2. The amount of self-emulsifying epoxy resin is from 30 to 70% by weight, based on the total weight of the dispersion, and the epoxy equivalent is
The epoxy resin dispersion according to claim 1, which is 450 to 2,500. 3. The epoxy compounds corresponding to A (a) and A (c) are polyglycidyl ethers based on polyhydric, especially dihydric phenols and / or novolaks.
Or a polyglycidyl ester.
The epoxy resin dispersion as described above. 4. The epoxy resin dispersion according to claim 3, wherein the polyhydric phenol is bisphenol A. 5. The epoxy resin dispersion according to claim 3, wherein the epoxy compound has an epoxy equivalent of 170 to 1,000. 6. The epoxy resin dispersion according to claim 1, wherein the aromatic polyol corresponding to A (b) is a polyhydric phenol. 7. An aliphatic polyol corresponding to A (c) is 60
The epoxy resin dispersion according to any one of claims 1 to 6, which is a polyalkylene glycol having an average molecular weight ( _Mw ) of 0 to 12,000. 8. The epoxy resin dispersion according to claim 1, wherein the amount of the isocyanate is 0.1 to 1.0% by weight based on the aliphatic polyol and the epoxy resin. 9. The epoxy resin dispersion according to claim 1, wherein the amount of A (c) is 4 to 9% by weight based on the total amount of the self-emulsifying epoxy resin. 10. Condensation product (c) wherein the equivalent ratio of OH-groups to epoxy groups is c1) 1: 0.85 to 1: 1.5, especially 1: 0.95.
~ 1: 1.20 and an epoxy equivalent of at least 100,00
0 or c2) the equivalent ratio is 1: 1.8 to 1: 3.5, especially 1: 2.0 to 1: 2.6 and the epoxy equivalent is 400 to 10,000.
The epoxy resin dispersion according to any one of claims 1 to 8, which is 0. 11. The method according to claim 1, wherein the amount of B) is 30 to 55% by weight.
The epoxy resin dispersion according to any one of Items 1 to 10. 12. The method according to claim 1, wherein the amount of C) is 2 to 15% by weight.
12. The epoxy resin dispersion according to any one of items 11 to 11. 13. Organic solvents corresponding to C) ethylene glycol mono- or diethers, propylene glycol mono- or diethers of monoalcohols having optionally branched alkyl groups having 1 to 6 carbon atoms, Butylene glycol mono- or diethers, optionally aliphatic alcohols, araliphatic and alicyclic alcohols having branched alkyl groups of 1 to 12 carbon atoms, aromatic compounds or ketones alone or The epoxy resin dispersion according to any one of claims 1 to 12, which is used in a mixed state. 14. The epoxy resin dispersion according to claim 1, wherein a basic or acidic curing agent is used as D). 15. The basic curing agent is an amine curing agent selected from the group consisting of polyoxypropylene amines, polyglycidyl ether / amine addition products and polyamidoamines, wherein said amine curing agent is 1: (0.75 15. The epoxy resin dispersion according to claim 14, which is used in an equivalent ratio of epoxy equivalent: amine hydrogen-equivalent of 1.5) to 1.5). 16. The epoxy resin dispersion according to claim 1, further comprising a thermosetting resin selected from the group consisting of amine- and / or phenolic resins as D). 17. The self-emulsifying epoxy resin has an average particle size of 0.
The epoxy resin dispersion according to any one of claims 1 to 16, which has a thickness of 3 to 0.8 µm. 18. The self-emulsifying epoxy resin A) is prepared by first reacting the three components A (a), A (b) and A (c) at elevated temperature in the presence of a condensation catalyst and optionally an organic solvent C). By addition of an optional organic solvent C) and then adding to the solution thus obtained an appropriate amount of water B) and the compound corresponding to D) by 30 to 30%. The method for producing an epoxy resin dispersion according to claim 1, wherein the addition is performed at 100 ° C under vigorous stirring. 19. The process as claimed in claim 18, wherein the condensation reaction is carried out at a temperature of from 120 to 220 ° C. and the organic solvent C) is added at from 30 to 150 ° C. 20. The method according to claim 18, wherein the compound corresponding to D) is added only immediately before use. 21. Use of the epoxy resin dispersion according to claim 1 for the production of paints, coatings, molding materials and thermosetting materials.